CN115445601B - Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof - Google Patents

Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof Download PDF

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CN115445601B
CN115445601B CN202210972453.5A CN202210972453A CN115445601B CN 115445601 B CN115445601 B CN 115445601B CN 202210972453 A CN202210972453 A CN 202210972453A CN 115445601 B CN115445601 B CN 115445601B
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CN115445601A (en
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丁靖
管国锋
唐百祥
万辉
李政
李会
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Nanjing Tech University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/04—Seven-membered rings not condensed with other rings

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Abstract

The invention provides a load type SiO 2 @M x O y ‑TiO 2 The catalyst, its preparation method and application, characterized in that the active component of the catalyst is M x O y The carrier is modified TiO 2 And the catalyst is coated with a layer of mesoporous SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the loading mass of the active component is 2.15-11.48% of the mass of the carrier; said M x O y Is CuO, snO 2 Or Fe (Fe) 2 O 3 One or more of them. The catalyst is used for catalyzing cyclohexanone to prepare epsilon-caprolactone, air is used as an oxygen source in the reaction, aldehyde is used as an auxiliary oxidant, the conversion rate of substrate cyclohexanone reaches 99%, and the highest yield of epsilon-caprolactone can reach 99%. The catalyst prepared by the method has the advantages of simple preparation, low cost, high activity, high selectivity, good stability and the like, is easy to separate from a product, has excellent repeatability and has good industrial application prospect.

Description

Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof
Technical Field
The invention relates to a load type SiO 2 @M x O y -TiO 2 The catalyst and its preparation process and application, especially in catalyzing the synthesis of epsilon-caprolactone with cyclohexanone.
Background
Polycaprolactone (PCL for short) is also called poly epsilon-caprolactone, is a high molecular organic polymer formed by ring-opening polymerization of epsilon-caprolactone monomer under the catalysis of metal anion complex catalyst, and can obtain different molecular weights by controlling polymerization conditions. The external appearance of the product is white solid powder, is nontoxic, insoluble in water and easily soluble in various polar organic solvents. PCL has good biocompatibility, good organic polymer compatibility and good biodegradability (can be biodegraded in soil and can be completely degraded into CO after 6-12 months) 2 And H 2 O, as a substitute material for daily plastic products, provides a viable path for solving plastic contamination), can be used as a cell growth support material, and is compatible with a variety of conventional plastics. In addition, PCL has good shape memory temperature control property, and is widely applied to the fields of production and processing of drug carriers, plasticizers, degradable plastics, nanofiber spinning and molding materials.
Epsilon-caprolactone is an important chemical intermediate as a monomer for synthesizing PCL, and is mainly applied to: synthetic poly epsilon-caprolactone, modified resin and polymer, and other lipids. Epsilon-caprolactone has an atmospheric boiling point of 235 ℃, a relative molecular mass of 114.14, a melting point of about-18 ℃ and a density of 1.029g/m 3 Colorless oily liquid, is easy to dissolve in water, ethanol and benzene, and is insoluble in petroleum ether. Epsilon-caprolactone has an unstable chemical structure, is easy to hydrolyze into caproic acid compounds under an acidic condition, is easy to hydrolyze into alcohol and ketone substances under an alkaline condition, and is prepared by Baeyer-Villiger reaction in industry.
The Baeyer-Villiger reaction was first discovered by Baeyer and Villiger at 1899, and subsequent researchers extended this study to find a number of cyclic ketones that can be oxidized by peroxy acids to lactones, and speculated on the mechanism of the reaction, which is named the Baeyer-Villiger oxidative rearrangement reaction. There are four major synthetic routes at present: 1. peroxy acid oxidation method 2, hydrogen peroxide oxidation method 3 and O 2 Aldehyde oxidation method 4, biological enzyme oxidation method. The international production generally uses the peroxyacid oxidation method to produce epsilon-caprolactone, but the process for producing peroxyacid is not mature because the process of peroxide in China is developed later,the peroxyacid has potential safety hazard in the production and transportation processes, and is not suitable for industrial production of domestic enterprises. The peroxy acid has extremely strong corrosion to equipment, extremely high corrosion resistance requirement to equipment, high equipment use and maintenance cost and serious environmental pollution. (Lu Qiaosen et al, development of caprolactone production Process [ J ]]Modern Chemical Industry 2015,35(2)：36-39)。
Compared with the peroxyacid oxidation method, the hydrogen peroxide oxidation method uses hydrogen peroxide as an oxidant to directly oxidize substrate cyclohexanone, so that the reaction flow is simplified, the method is environment-friendly, and the potential safety hazard is reduced. Because high-concentration hydrogen peroxide is easy to explode, low-concentration hydrogen peroxide is widely used as an oxidant at present, but the oxidation capability of the low-concentration hydrogen peroxide is weak, excessive hydrogen peroxide is needed to participate in the reaction, partial hydrogen peroxide is decomposed in an ineffective way, so that the hydrogen peroxide utilization rate is low, and water in a system can hydrolyze epsilon-caprolactone. By O 2 In theory, the aldehyde oxidation method can completely convert cyclohexanone into lactone, meets the requirements of modern green chemical production, has high epsilon-caprolactone yield and safer production, and therefore, O 2 The aldehyde oxidation process has great research value. In patent grant publication No. CN105440006B (a method for preparing epsilon-caprolactone by catalyzing cyclohexanone by soluble salt modified magnesium aluminum hydrotalcite) and patent grant publication No. CN104003971B (a method for preparing epsilon-caprolactone by catalyzing cyclohexanone by oxidation), the oxidation of cyclohexanone is catalyzed by oxygen as an oxygen source, and the yield of synthesized epsilon-caprolactone is high. If the high-concentration oxygen is applied to industrial production, the high-concentration oxygen still has a certain danger, and the air is used as an oxygen source, so that the cost can be reduced, and the danger in the production process can be reduced to the minimum, but the volume fraction of the oxygen in the air is only about 21%, the oxidation capability is weaker, and the oxidation reaction is difficult to carry out under the condition of not adding a catalyst, so that the efficient catalyst needs to be designed and developed.
Disclosure of Invention
One object of the present invention is to provide a supported SiO which improves the deficiencies of the prior art 2 @M x O y -TiO 2 A catalyst; another object of the present invention is to provide a process for preparing the above catalyst, and a further object of the present invention is toThe application of the catalyst in catalyzing cyclohexanone to synthesize epsilon-caprolactone is provided.
The technical scheme of the invention is as follows: load type SiO 2 @M x O y -TiO 2 The catalyst is characterized in that the active component of the catalyst is M x O y The carrier is modified TiO 2 And the catalyst is coated with a layer of mesoporous SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the loading mass of the active component is 2.15-11.48% of the mass of the carrier; said M x O y Is CuO, snO 2 Or Fe (Fe) 2 O 3 One or more of them.
Preferably said modified TiO 2 Has a specific surface area of 80-120m 2 And/g, the average pore diameter is 10-20nm, and the particle size is 40-100nm.
The invention also provides a method for preparing the catalyst, which comprises the following specific steps:
(1) Ti (SO) 4 ) 2 With NH 4 Adding Cl into ethanol water solution, stirring thoroughly, performing hydrothermal reaction, naturally cooling, separating, washing, drying, and roasting to obtain TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in dilute acetic acid solution, condensing and refluxing, separating, washing and drying to obtain modified TiO 2 A microsphere;
(2) Modified TiO 2 Adding microspheres, a template agent and inorganic metal salt into an ethanol water solution, uniformly mixing, dropwise adding ammonia water to adjust the solution to be alkaline, fully stirring, dropwise adding TEOS into the solution, and using the ammonia water to maintain the solution to be alkaline; then carrying out hydrothermal reaction, naturally cooling, separating, washing, drying and roasting to obtain SiO 2 @M x O y -TiO 2 A catalyst.
Preferably Ti (SO) added in step (1) 4 ) 2 With NH 4 The mass ratio of Cl is 1: (0.1-1), the volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1: (0.25-4%), ti (SO) 4 ) 2 The mass ratio of the aqueous ethanol solution to the aqueous ethanol solution is 1: (34.6-53.2); the hydrothermal temperature is 100-200 ℃, and the hydrothermal time is 2-12 h; the roasting temperature is 400-600 ℃, the heating rate is 1-5 ℃/min, and the roasting time is 2-6 h;the mass concentration of acetic acid in the dilute acetic acid solution is 1-10%; the condensing reflux temperature is 40-80 ℃, and the condensing reflux time is 12-24 hours; the drying temperature is 60-100 ℃ and the drying time is 6-24 h.
Preferably, the template agent in the step (2) is any one of CTAB, P123 or F127; the inorganic metal salt is Cu (NO) 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 O、Fe 2 (NO 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O or SnCl 4 ·5H 2 One or more of O.
Preferably the modified TiO added in step (2) 2 The mass ratio of the microsphere, the template agent, the inorganic metal salt and TEOS is 1: (0.2-2): (0.05-0.3): (0.5-5); the volume ratio of deionized water to ethanol in the ethanol water solution is 1: (0.25-4); modified TiO 2 The mass ratio of the aqueous ethanol solution to the aqueous ethanol solution is 1: (84.15-191.3); the mass concentration of the ammonia water is 10-25%, and the pH value of the solution is regulated and maintained at 8-12; the hydrothermal temperature is 100-200 ℃, and the hydrothermal time is 12-48 h; the drying temperature is 60-100 ℃ and the drying time is 6-24 h; the roasting temperature is 400-800 ℃, the heating rate is 1-5 ℃/min, and the roasting time is 2-6 h.
The invention also provides the load type SiO 2 @M x O y -TiO 2 The catalyst is applied to catalyzing cyclohexanone to synthesize epsilon-caprolactone. The method comprises the following specific steps: sequentially adding load type SiO into a three-neck flask 2 @M x O y -TiO 2 The catalyst, cyclohexanone, a co-oxidant and a solvent are introduced into the reactor by using a bubbling method, then the reaction is started, and after the reaction is finished, the catalyst is centrifugally separated; wherein the mass ratio of the cyclohexanone to the auxiliary oxidant to the solvent is 1: (1-4): (20-60), the catalyst dosage is 5-25% of the mass of the added cyclohexanone; the auxiliary oxidant is benzaldehyde; the solvent is 1, 2-dichloroethane; the air flow rate is 10-60 mL/min, the reaction temperature is 20-80 ℃, and the reaction time is 2-12 h.
The beneficial effects are that: loading active ingredients on modified TiO by screening suitable active ingredients 2 On the microsphere, dilute acetic acid is used for pickling modified TiO 2 Microsphere can be liftedHigh dispersivity of active components and acting force between carriers, and modified TiO 2 As a co-catalyst to facilitate the reaction, to further prevent the active component M x O y (M x O y Is CuO, snO 2 、Fe 2 O 3 One or more) are dissolved out due to the corrosion of byproduct acid in the reaction system, and a layer of mesoporous SiO is coated on the outer layer of the catalyst 2 Inhibiting the falling of the active component improves the stability of the catalyst.
Detailed Description
The present invention will be described in more detail with reference to examples. These examples are merely illustrative of the best modes of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
SiO 2 @CuO-TiO 2 Is prepared from
Step 1. 2.4g of Ti (SO 4 ) 2 And 0.24gNH 4 Cl is added into 83.10g solution composed of 20mL deionized water and 80mL ethanol, and fully stirred; transferring the mixed solution into a hydrothermal kettle to react for 2 hours at 100 ℃, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying for 6 hours at 80 ℃, heating to 400 ℃ at 1 ℃/min, and roasting for 6 hours to obtain the TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in 100mL10wt.% dilute acetic acid solution, condensing and refluxing at 80 ℃ for 12h, separating, washing, and drying at 80 ℃ for 6h to obtain the product with a specific surface area of 102m 2 Modified TiO with average pore diameter of 14nm and particle size of 60nm 2 And (3) microspheres.
Step 2. 0.50g of modified TiO 2 Microspheres, 1.0gCTAB, 0.10gCu (NO) 3 ) 2 NO 3 ·3H 2 Adding O into 83.10g of solution consisting of 20mL of deionized water and 80mL of ethanol, uniformly mixing, dropwise adding 10wt.% of ammonia water to adjust the pH of the solution to 12, fully stirring, dropwise adding 0.50g of TEOS into the mixed solution, maintaining the pH of the solution to 12 by using 10wt.% of ammonia water, and fully stirring; transferring the mixed solution to a hydrothermal kettle at 100 ℃ for reaction for 48 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 100 ℃ for 6 hours, heating to 400 ℃ at 1 ℃/min, and roasting for 6 hours to obtain SiO 2 @CuO-TiO 2 The catalyst (active component loading was 6.58 wt).％)。
Example 2
SiO 2 @Fe 2 O 3 -TiO 2 Is prepared from
Step 1. 1.8g of Ti (SO 4 ) 2 And 1.8gNH 4 Cl is added into 95.63g solution composed of 80mL deionized water and 20mL ethanol, and the mixture is fully stirred; transferring the mixed solution into a hydrothermal kettle to react for 2 hours at 200 ℃, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 60 ℃ for 24 hours, heating to 550 ℃ at 5 ℃/min, and roasting for 2 hours to obtain the TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in 100mL1wt.% dilute acetic acid solution, condensing and refluxing at 40 ℃ for 24 hours, separating, washing, and drying at 60 ℃ for 24 hours to obtain the product with the specific surface area of 80m 2 Modified TiO with average pore diameter of 20nm and particle size of 100nm 2 And (3) microspheres.
Step 2. 0.50g of modified TiO 2 Microspheres, 0.50g CTAB, 0.05g Fe 2 (NO 3 ) 3 ·9H 2 O is added into 95.63g of solution composed of 80mL of deionized water and 20mL of ethanol, the mixture is uniformly mixed, 15wt.% of ammonia water is added dropwise to adjust the pH of the solution to 8, the mixture is fully stirred, 0.25g of TEOS is added dropwise into the mixed solution, the pH of the solution is maintained to 8 by 15wt.% of ammonia water, and the mixture is fully stirred; transferring the mixed solution to a hydrothermal kettle for reaction at 200 ℃ for 12 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 60 ℃ for 24 hours, heating to 800 ℃ at 5 ℃/min, and roasting for 6 hours to obtain SiO 2 @Fe 2 O 3 -TiO 2 Catalyst (active component loading of 3.95 wt.%).
Example 3
SiO 2 @SnO 2 -TiO 2 Is prepared from
Step 1. 2.4g of Ti (SO 4 ) 2 And 1.2gNH 4 Cl is added into 84.15g solution composed of 25mL deionized water and 75mL ethanol, and the mixture is fully stirred; transferring the mixed solution into a hydrothermal kettle for reaction at 120 ℃ for 12 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 100 ℃ for 12 hours, heating to 600 ℃ at 5 ℃/min, and roasting for 2 hours to obtain the TiO 2 A microsphere; tiO is mixed with 2 The microspheres were dispersed in 100mL of 5wt.% dilute acetic acid solution, refluxed for 18h at 60 ℃, separated, washed, 10Drying at 0deg.C for 12 hr to obtain a specific surface area of 91m 2 Modified TiO with average pore diameter of 12nm and particle size of 70nm 2 And (3) microspheres.
Step 2. 1.0g of modified TiO 2 Microspheres, 0.20g P123, 0.05g SnCl 4 ·5H 2 Adding O into 84.15g of solution consisting of 25mL of deionized water and 75mL of ethanol, uniformly mixing, dropwise adding 20wt.% of ammonia water to adjust the pH of the solution to 10, fully stirring, dropwise adding 5.0g of TEOS into the mixed solution, maintaining the pH of the solution to 10 by using 20wt.% of ammonia water, and fully stirring; transferring the mixed solution to a hydrothermal kettle for reaction at 120 ℃ for 48 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 100 ℃ for 24 hours, heating to 600 ℃ at 1 ℃/min, and roasting for 6 hours to obtain SiO 2 @SnO 2 -TiO 2 Catalyst (active component loading of 2.15 wt.%).
Example 4
SiO 2 @CuO/SnO 2 -TiO 2 Is prepared from
Step 1. 2.4g of Ti (SO 4 ) 2 And 1.8gNH 4 Cl is added into 94.58g solution composed of 75mL deionized water and 25mL ethanol, and the mixture is fully stirred; transferring the mixed solution into a hydrothermal kettle for reaction at 160 ℃ for 2 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 80 ℃ for 12 hours, heating to 550 ℃ at 2 ℃/min, and roasting for 2 hours to obtain the TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in 100mL10wt.% dilute acetic acid solution, condensing and refluxing at 80deg.C for 24 hr, separating, washing, and drying at 80deg.C for 12 hr to obtain a specific surface area of 85m 2 Modified TiO with average pore diameter of 10nm and particle size of 90nm 2 And (3) microspheres.
Step 2. 1.0g of modified TiO 2 Microspheres, 1.00g F127, 0.20g CuCl 2 ·2H 2 O、0.05gSnCl 4 ·5H 2 Adding O into 94.58g of solution consisting of 75mL of deionized water and 25mL of ethanol, uniformly mixing, dropwise adding 25wt.% of ammonia water to adjust the pH of the solution to 10, fully stirring, dropwise adding 2.0g of TEOS into the mixed solution, maintaining the pH of the solution to 10 by using 25wt.% of ammonia water, and fully stirring; transferring the mixed solution to a hydrothermal kettle for reaction at 120 ℃ for 48 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 80 ℃ for 12 hours, and heating at 2 ℃/min to the temperatureRoasting at 550 ℃ for 6 hours to obtain SiO 2 @CuO/SnO 2 -TiO 2 Catalyst (active component loading 11.48 wt.%).
Example 5
SiO 2 @Fe 2 O 3 /SnO 2 -TiO 2 Is prepared from
Step 1. 2.4g of Ti (SO 4 ) 2 And 1.8gNH 4 Cl is added into 89.37g solution composed of 50mL deionized water and 50mL ethanol, and the mixture is fully stirred; transferring the mixed solution into a hydrothermal kettle to react for 2 hours at 180 ℃, naturally cooling, separating, washing, drying at 80 ℃ for 12 hours, heating to 500 ℃ at 5 ℃/min, and roasting for 4 hours to obtain the TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in 100mL10wt.% dilute acetic acid solution, condensing and refluxing at 80deg.C for 24 hr, separating, washing, and drying at 80deg.C for 12 hr to obtain a specific surface area of 120m 2 Modified TiO with average pore diameter of 16nm and particle size of 40nm 2 And (3) microspheres.
Step 2. 1.0g of modified TiO 2 Microspheres, 1.00g CTAB, 0.20g FeCl 3 ·6H 2 O、0.10gSnCl 4 ·5H 2 O is added into 89.37g of solution composed of 50mL of deionized water and 50mL of ethanol, the mixture is uniformly mixed, 25wt.% of ammonia water is added dropwise to adjust the pH of the solution to 10, the mixture is fully stirred, 2.5g of TEOS is added dropwise into the mixed solution, the pH of the solution is maintained to 10 by 25wt.% of ammonia water, and the mixture is fully stirred; transferring the mixed solution to a hydrothermal kettle at 160 ℃ for reaction for 24 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 80 ℃ for 12 hours, heating to 500 ℃ at 2 ℃/min, and roasting for 6 hours to obtain SiO 2 @Fe 2 O 3 /SnO 2 -TiO 2 Catalyst (active component loading 10.21 wt.%).
Example 6
Fe 2 O 3 /CuO-TiO 2 @SiO 2 Is prepared from
Step 1. 2.4g of Ti (SO 4 ) 2 And 1.8gNH 4 Adding Cl into 89.37g solution composed of 50mL deionized water and 50mL ethanol, stirring thoroughly, transferring the mixed solution into a hydrothermal kettle, reacting at 180deg.C for 2h, cooling naturally, separating, washing, and drying at 80deg.CHeating to 550 ℃ at a speed of 2 ℃/min for 12h, and roasting for 6h to obtain TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in 100mL10wt.% dilute acetic acid solution, condensing and refluxing at 80deg.C for 24 hr, separating, washing, and drying at 80deg.C for 12 hr to obtain a specific surface area of 120m 2 Modified TiO with average pore diameter of 16nm and particle size of 40nm 2 And (3) microspheres.
Step 2. 1.0g of modified TiO 2 Microspheres, 1.0g CTAB, 0.05g Fe 2 (NO 3 ) 3 ·9H 2 O、0.15gCu(NO 3 ) 2 ·3H 2 O is added into 89.37g of solution composed of 50mL of deionized water and 50mL of ethanol, the mixture is uniformly mixed, 25wt.% of ammonia water is then added dropwise to adjust the pH of the solution to 10, the mixture is fully stirred, 4.5g of TEOS is added dropwise to the mixed solution, the pH of the solution is maintained to 10 by 25wt.% of ammonia water, and the mixture is fully stirred; transferring the mixed solution to a hydrothermal kettle for reaction at 120 ℃ for 24 hours, naturally cooling, separating and washing after the hydrothermal reaction is finished, drying at 80 ℃ for 12 hours, heating to 550 ℃ at 2 ℃/min, and roasting for 6 hours to obtain SiO 2 @Fe 2 O 3 /CuO-TiO 2 Catalyst (active component loading of 6.92 wt.%).
Supported SiO 2 @M x O y -TiO 2 The catalyst catalyzes cyclohexanone to synthesize epsilon-caprolactone:
application example 1
Sequentially adding SiO into a three-neck flask 2 @CuO-TiO 2 Catalyst (0.10 g), cyclohexanone (1.0 g), auxiliary oxidant benzaldehyde (1.0 g) and solvent 1, 2-dichloroethane (20 g) were introduced into 30mL/min of air and reacted at 30℃for 8 hours. The obtained product was subjected to gas chromatography with a selectivity of 99.15% and a yield of 80.21%.
Application example 2
Sequentially adding SiO into a three-neck flask 2 @Fe 2 O 3 -TiO 2 Catalyst (0.05 g), cyclohexanone (1.0 g), auxiliary oxidant benzaldehyde (2.0 g) and solvent 1, 2-dichloroethane (20 g), and introducing 10mL/min of air to react for 4h at 70 ℃. The obtained product was subjected to gas chromatography with a selectivity of 96.89% and a yield of 75.26%.
Application example 3
Sequentially adding SiO into a three-neck flask 2 @SnO 2 -TiO 2 Catalyst (0.25 g), cyclohexanone (1.0 g), auxiliary oxidant benzaldehyde (4.0 g) and solvent 1, 2-dichloroethane (60 g) were introduced into air at 40mL/min and reacted for 12h at 20 ℃. The obtained product was subjected to gas chromatography with a selectivity of 97.53% and a yield of 73.25%.
Application example 4
Sequentially adding SiO into a three-neck flask 2 @CuO/SnO 2 -TiO 2 Catalyst (0.15 g), cyclohexanone (1.0 g), auxiliary oxidant benzaldehyde (3.0 g) and solvent 1, 2-dichloroethane (40 g) were introduced into air at 50mL/min and reacted at 40℃for 8 hours. The obtained product was subjected to gas chromatography with a selectivity of 98.62% and a yield of 95.31%.
Application example 5
Sequentially adding SiO into a three-neck flask 2 @Fe 2 O 3 /SnO 2 -TiO 2 Catalyst (0.25 g), cyclohexanone (1.0 g), auxiliary oxidant benzaldehyde (4.0 g) and solvent 1, 2-dichloroethane (50 g) were introduced into 40mL/min of air and reacted at 80℃for 3 hours. The obtained product was subjected to gas chromatography with a selectivity of 97.23% and a yield of 89.82%.
Application example 6
Sequentially adding SiO into a three-neck flask 2 @Fe 2 O 3 /CuO-TiO 2 Catalyst (0.05 g), cyclohexanone (0.50 g), auxiliary oxidant benzaldehyde (1.0 g) and solvent 1, 2-dichloroethane (15 g), and air (60 mL/min) was introduced for reaction at 50 ℃ for 5h. The obtained product was subjected to gas chromatography with a selectivity of 99.58% and a yield of 99.21%.
Table 1 comparison of experimental results of application examples

Claims (7)

1. Load type SiO 2 @M x O y -TiO 2 A catalyst characterized in that said catalyst is activeThe sexual component is M x O y The carrier is modified TiO 2 And the catalyst is coated with a layer of mesoporous SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the loading mass of the active component is 2.15-11.48% of the mass of the carrier; said M x O y Is CuO, snO 2 Or Fe (Fe) 2 O 3 One or more of them; the preparation method comprises the following specific steps:
(1) Ti (SO) 4 ) 2 With NH 4 Adding Cl into ethanol water solution, stirring thoroughly, performing hydrothermal reaction, naturally cooling, separating, washing, drying, and roasting to obtain TiO 2 A microsphere; tiO is mixed with 2 Dispersing the microspheres in dilute acetic acid solution, condensing and refluxing, separating, washing and drying to obtain modified TiO 2 A microsphere;
(2) Modified TiO 2 Adding microspheres, a template agent and inorganic metal salt into an ethanol water solution, uniformly mixing, dropwise adding ammonia water to adjust the solution to be alkaline, fully stirring, dropwise adding TEOS into the solution, and using the ammonia water to maintain the solution to be alkaline; then carrying out hydrothermal reaction, naturally cooling, separating, washing, drying and roasting to obtain SiO 2 @M x O y -TiO 2 A catalyst.
2. The supported SiO of claim 1 2 @M x O y -TiO 2 Catalyst characterized in that the modified TiO 2 Has a specific surface area of 80-120m 2 And/g, the average pore diameter is 10-20nm, and the particle size is 40-100nm.
3. The supported SiO according to claim 1 2 @M x O y -TiO 2 The catalyst is characterized in that: ti (SO) added in step (1) 4 ) 2 With NH 4 The mass ratio of Cl is 1: (0.1-1), the volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1: (0.25-4%), ti (SO) 4 ) 2 The mass ratio of the aqueous ethanol solution to the aqueous ethanol solution is 1: (34.6-53.2); the hydrothermal temperature is 100-200 ℃, and the hydrothermal time is 2-12 h; the roasting temperature is 400-600 ℃, the heating rate is 1-5 ℃/min, and the roasting time is2-6 h; the mass percentage concentration of acetic acid in the dilute acetic acid solution is 1-10%; the condensing reflux temperature is 40-80 ℃, and the condensing reflux time is 12-24 hours; the drying temperature is 60-100 ℃ and the drying time is 6-24 h.
4. The supported SiO according to claim 1 2 @M x O y -TiO 2 The catalyst is characterized in that: the template agent in the step (2) is any one of CTAB, P123 or F127; the inorganic metal salt is Cu (NO) 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 O、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O or SnCl 4 ·5H 2 One or more of O.
5. The supported SiO according to claim 1 2 @M x O y -TiO 2 The catalyst is characterized in that: modified TiO added in the step (2) 2 The mass ratio of the microsphere, the template agent, the inorganic metal salt and TEOS is 1: (0.2-2): (0.05-0.3): (0.5-5); the volume ratio of deionized water to ethanol in the ethanol water solution is 1: (0.25-4); modified TiO 2 The mass ratio of the aqueous ethanol solution to the aqueous ethanol solution is 1: (84.15-191.3); the mass percentage concentration of the ammonia water is 10-25%, and the pH value of the solution is regulated and maintained at 8-12; the hydrothermal temperature is 100-200 ℃, and the hydrothermal time is 12-48 h; the drying temperature is 60-100 ℃ and the drying time is 6-24 h; the roasting temperature is 400-800 ℃, the heating rate is 1-5 ℃/min, and the roasting time is 2-6 h.
6. A supported SiO as claimed in claim 1 2 @M x O y -TiO 2 The catalyst is applied to catalyzing cyclohexanone to synthesize epsilon-caprolactone.
7. The application according to claim 6, which comprises the following specific steps: sequentially adding load type SiO into a three-neck flask 2 @M x O y -TiO 2 Catalyst, cyclohexanone, auxiliary oxidant and solvent, and air is introduced by bubbling methodStarting reaction, and centrifugally separating out a catalyst after the reaction is finished; wherein the mass ratio of the cyclohexanone to the auxiliary oxidant to the solvent is 1: (1-4): (20-60), the catalyst dosage is 5-25% of the mass of the added cyclohexanone; the auxiliary oxidant is benzaldehyde; the solvent is 1, 2-dichloroethane; the air flow rate is 10-60 mL/min, the reaction temperature is 20-80 ℃, and the reaction time is 2-12 h.
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GB1107292A (en) * 1965-02-03 1968-03-27 Stamicarbon The preparation of ªŠ-caprolactone
CN105233854A (en) * 2015-11-02 2016-01-13 兰州大学 Catalyst for preparing epsilon-caprolactone and preparation method
CN107308944A (en) * 2017-05-05 2017-11-03 浙江大学 A kind of TiO 2-based catalyst and its preparation method and application
CN109879853A (en) * 2019-01-27 2019-06-14 台州市源众药业有限公司 A kind of Fe2O3/CeO2The method that catalysis of pimelinketone oxidation prepares 6-caprolactone
CN112742415A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 TiO 22Nanotube composite copper-based silicon-based catalyst, preparation method and application thereof
CN112844404A (en) * 2021-01-29 2021-05-28 西南化工研究设计院有限公司 Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof
CN114054083A (en) * 2021-10-22 2022-02-18 浙江大学衢州研究院 Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1107292A (en) * 1965-02-03 1968-03-27 Stamicarbon The preparation of ªŠ-caprolactone
CN105233854A (en) * 2015-11-02 2016-01-13 兰州大学 Catalyst for preparing epsilon-caprolactone and preparation method
CN107308944A (en) * 2017-05-05 2017-11-03 浙江大学 A kind of TiO 2-based catalyst and its preparation method and application
CN109879853A (en) * 2019-01-27 2019-06-14 台州市源众药业有限公司 A kind of Fe2O3/CeO2The method that catalysis of pimelinketone oxidation prepares 6-caprolactone
CN112742415A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 TiO 22Nanotube composite copper-based silicon-based catalyst, preparation method and application thereof
CN112844404A (en) * 2021-01-29 2021-05-28 西南化工研究设计院有限公司 Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof
CN114054083A (en) * 2021-10-22 2022-02-18 浙江大学衢州研究院 Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof

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